242
Bull. Chem. Soc. Jpn. Vol. 85, No. 2 (2012)
Butadiyne with Trialkoxyphenylurethane Groups
¹1
with ether. The ether layer was collected and dried over
anhydrous magnesium sulfate. After filtration, solvent of the
filtrate was removed under reduced pressure to give 1.79 g
(96%) of 3a as colorless solid: IR (KBr): 2923, 2854, 1681,
1225, 1122, 721 cm ;
1H NMR (400 MHz, CDCl3): ¤ 0.88
(9H, t, J = 6.9 Hz), 1.20-1.52 (54H, m), 1.72 (2H, tt, J = 7.6,
6.6 Hz), 1.79 (4H, tt, J = 7.6, 6.6 Hz), 3.90 (2H, t, J = 6.6 Hz),
3.92 (4H, t, J = 6.6 Hz), 6.27 (2H, s); 13C NMR (100 MHz,
CDCl3): ¤ 14.11, 22.69, 26.03, 26.10, 29.24, 29.37, 29.63,
29.65, 29.69, 29.73, 30.26, 31.92, 69.16, 73.54, 103.41,
124.33, 128.38, 136.22, 153.48.
3,4,5-Trimethoxyphenyl Isocyanate (5b): Sodium azide
(2.9 g, 45 mmol) and benzyltriethylammonium chloride
(500 mg, 2.2 mmol) were dissolved in water (15 mL), and
the solution was cooled in an ice bath. To this solution, 4b
(5.5 g, 24 mmol) in the mixture of toluene (30 mL) was added
dropwise. By controlling the addition rate of the solution of 4b,
the temperature of the reaction mixture was kept between
10 and 15 °C. After finishing the addition, the mixture was
stirred over night, and it was extracted with toluene. The
organic layers were combined and dried over anhydrous
magnesium sulfate. The filtrate was heated at 80 °C, and
1
1589, 1431, 1335, 1225, 1126, 725 cm¹1; H NMR (400 MHz,
CDCl3): ¤ 0.88 (9H, t, J = 6.8 Hz), 1.20-1.52 (54H, m), 1.75
(2H, tt, J = 7.6, 6.6 Hz), 1.82 (4H, tt, J = 7.3, 6.6 Hz), 4.02
(4H, t, J = 6.6 Hz), 4.04 (2H, t, J = 6.6 Hz), 7.32 (2H, s), a
carboxyl proton was not clearly detected; 13C NMR (100 MHz,
CDCl3): ¤ 14.07, 22.68, 26.04, 26.07, 29.28, 29.37, 29.38,
29.56, 29.63, 29.65, 29.69, 30.32, 31.92, 69.15, 73.51, 108.54,
123.72, 143.13, 152.82, 172.02.
3,4,5-Trimethoxybenzoic Acid (3b):
Ester 2b (7.23 g,
3.2 mmol) was dissolved in 100 mL of ethanol. To this solution,
potassium hydroxide (0.36 g, 6.4 mmol) in 50 mL of water was
added, and it was refluxed for 3 h. After evaporating ethanol,
diluted sulfuric acid was added and the mixture was extracted
with ether. The ether layer was collected and dried over
anhydrous magnesium sulfate. After filtration, solvent of the
filtrate was removed under reduced pressure to give 6.45 g
solvent of the solution was removed to give 4.9 g (98%) of 5b:
¹1
IR (KBr): 2927, 2854, 2271, 1645, 1593, 1232, 1132 cm
;
(95%) of 3b as colorless solid: IR (KBr): 2958, 2839, 1687,
1H NMR (400 MHz, CDCl3): ¤ 3.82 (3H, s), 3.84 (6H, s), 6.32
(2H, s); 13C NMR (100 MHz, CDCl3): ¤ 56.07, 60.85, 102.11,
124.37, 128.92, 136.02, 153.54.
¹1
1589, 1417, 1329, 1227, 1130 cm
;
1H NMR (400 MHz,
CDCl3): ¤ 3.93 (6H, s), 3.94 (3H, s), 7.38 (2H, s), a carboxyl
proton was not clearly detected; 13C NMR (100 MHz, CDCl3):
¤ 56.21, 60.91, 107.40, 124.09, 142.97, 152.93, 171.80.
3,4,5-Tridodecyloxybenzoyl Chloride (4a): To 3a (6.81 g,
10 mmol), thionyl chloride (4.0 g, 34 mmol) was added drop-
wise and the mixture was stirred at 80 °C for 2 h. Thionyl
chloride remained in the mixture was removed by distillation
4,6-Decadiyn-1,10-diol (8):
To the mixture of acetone
(60 mL), copper(I) chloride (0.269 g, 2.7 mmol), and N,N,N¤,N¤-
tetramethylethylenediamine (TMEDA) (0.362 g, 3.1 mmol), 4-
pentyn-1-ol (6) (2.0 g, 23.8 mmol) was added, and it was heated
at 80 °C with oxygen bubbling for 20 h. Diluted hydrochloric
acid was added to the reaction mixture and it was extracted
with chloroform. The organic layers were collected and dried
over anhydrous magnesium sulfate. After filtration, solvent of
the filtrate was evaporated under reduced pressure. The residue
was purified by the column chromatography (silica gel,
hexane-ethyl acetate (3:7)) to give 1.62 g (82%) of 8 as color-
to give 6.91 g (99%) of 4a as colorless solid: IR (KBr): 2924,
¹1
2850, 1751, 1581, 1427, 1335, 1126, 771 cm
;
1H NMR
(400 MHz, CDCl3): ¤ 0.88 (9H, t, J = 6.8 Hz), 1.20-1.52 (54H,
m), 1.74 (2H, tt, J = 7.6, 6.5 Hz), 1.82 (4H, tt, J = 7.4, 6.5 Hz),
4.02 (4H, t, J = 6.5 Hz), 4.08 (2H, t, J = 6.5 Hz), 7.33 (2H, s);
13C NMR (100 MHz, CDCl3): ¤ 14.11, 22.68, 25.97, 26.03,
29.17, 29.36, 29.51, 29.61, 29.65, 29.68, 30.31, 31.92, 69.30,
73.70, 109.92, 127.23, 144.68, 152.83, 167.72.
3,4,5-Trimethoxybenzoyl Chloride (4b): To 3b (5.04 g,
24 mmol), thionyl chloride (9.57 g, 80 mmol) was added
dropwise and the mixture was stirred at 80 °C for 21 h. Thionyl
chloride remained in the mixture was removed by distillation
to give 5.09 g (93%) of 4b as colorless solid: IR (KBr): 2969,
2837, 1763, 1591, 1444, 1340, 1132 cm¹1; 1H NMR (400 MHz,
CDCl3): ¤ 3.93 (6H, s), 3.97 (3H, s), 7.38 (2H, s); 13C NMR
(100 MHz, CDCl3): ¤ 56.19, 60.91, 108.66, 127.47, 144.31,
152.78, 167.38.
1
less solid: H NMR (400 MHz, CDCl3): ¤ 1.54 (2H, broad s),
1.78 (4H, tt, J = 7.0, 6.1 Hz), 2.39 (4H, t, J = 7.0 Hz), 3.75
(4H, t, J = 6.1 Hz); 13C NMR (100 MHz, CDCl3): ¤ 15.70,
30.90, 61.40, 65.61, 76.77.
5,7-Decadiyn-1,12-diol (9):
To the mixture of acetone
(60 mL), copper(I) chloride (0.208 g, 2.0 mmol), and TMEDA
(0.317 g, 2.7 mmol), 4-hexyn-1-ol (7) (2.0 g, 20 mmol) was
added, and it was heated at 80 °C with oxygen bubbling for
20 h. Diluted hydrochloric acid was added to the reaction
mixture and it was extracted with chloroform. The organic
layers were collected and dried over anhydrous magnesium
sulfate. After filtration, solvent of the filtrate was evaporated
under reduced pressure. The residue was purified by the
column chromatography (silica gel, chloroform-ethyl acetate
3,4,5-Tridodecyloxyphenyl Isocyanate (5a):
Sodium
azide (2.5 g, 38 mmol) and benzyltriethylammonium chloride
(1.2 g, 5 mmol) were dissolved in water (15 mL), and the
solution was cooled in an ice bath. To this solution, 4a (5 g,
7.2 mmol) in the mixture of acetone (15 mL) and toluene
(10 mL) was added dropwise. By controlling the addition rate
of the solution of 4a, the temperature of the reaction mixture
was kept between 10 and 15 °C. After finishing the addition,
the mixture was stirred over night, and it was extracted with
toluene. The organic layers were combined and dried over
anhydrous magnesium sulfate. The filtrate was heated at 80 °C,
and solvent of the solution was removed to give 4.06 g (84%)
of 5a: IR (KBr): 2954, 2850, 2279, 1643, 1467, 1438, 1385,
1
(3:2)) to give 1.63 g (82%) of 9 as colorless solid: H NMR
(400 MHz, CDCl3): ¤ 1.45-1.73 (10H, m), 2.31 (4H, t, J =
6.6 Hz), 3.68 (4H, t, J = 6.2 Hz); 13C NMR (100 MHz, CDCl3):
¤ 18.94, 24.54, 31.66, 62.24, 65.54, 77.16.
4,6-Decadiyn-1,10-diyl
Bis[N-(3,4,5-tridodecyloxy-
phenyl)carbamate] (10a): To toluene (30 mL), 5a (1.38 g,
2.1 mmol), 8 (0.16 g, 0.96 mmol), and three drops of dibutyltin
didodecanoate were added and the mixture was stirred at
100 °C for 5 h. After removing the solvent under reduced
pressure, the residue was purified by the column chromatog-
raphy (silica gel, hexane-ethyl acetate (9:1)) to give 1.29 g